CN109690364B

CN109690364B - Antifouling film

Info

Publication number: CN109690364B
Application number: CN201780052020.5A
Authority: CN
Inventors: 芝井康博; 厚母贤; 中松健一郎
Original assignee: Sharp Corp
Current assignee: Sharp Corp
Priority date: 2016-08-25
Filing date: 2017-06-28
Publication date: 2020-11-10
Anticipated expiration: 2037-06-28
Also published as: JPWO2018037711A1; US10976475B1; WO2018037711A1; CN109690364A; US20210096282A1; JP6600414B2

Abstract

The invention provides an antifouling film having excellent antifouling property, adhesion, abrasion resistance and reliability. The antifouling film of the present invention comprises: a substrate; and a polymer layer which is disposed on the surface of the base material and has a concavo-convex structure having a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light on the surface, wherein the polymer layer is a cured product of a polymerizable composition containing, in terms of active ingredients, 15 to 40 wt% of hexafunctional or higher acrylic urethane, 35 to 60 wt% of tetrafunctional or higher polyfunctional acrylate having 3 to 15 ethylene oxide groups per functional group, 15 to 30 wt% of monofunctional acrylate having no ethylene oxide group, 0.5 to 10 wt% of a fluorine-based release agent having a perfluoropolyether group and having a fluorine atom concentration of 50 wt% or less, and 0.5 to 5 wt% of a polymerization initiator.

Description

Antifouling film

Technical Field

The present invention relates to an antifouling film. More specifically, the present invention relates to an antifouling film having a nano-sized uneven structure.

Background

Various studies have been made on optical films having antireflection properties (see, for example, patent documents 1 to 3). In particular, an optical film having a nano-sized relief structure (nanostructure) is known to have excellent antireflection properties. According to such an uneven structure, the refractive index changes continuously from the air layer to the substrate, and therefore reflected light can be significantly reduced.

Documents of the prior art

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2012-52125

[ patent document 2] International publication No. 2007/040159

[ patent document 3] Japanese patent laid-open No. 2005-97371

Disclosure of Invention

Technical problem to be solved by the invention

However, although such an optical film has excellent antireflection properties, the uneven structure on the surface thereof causes stains such as fingerprints (sebum) to spread easily when the stains are adhered thereto, and it is difficult to wipe off the stains entering between the convex portions. Moreover, the attached dirt is easily visible because its reflectance is greatly different from that of the optical film. Therefore, a functional film (antifouling film) having a nano-sized uneven structure on the surface and excellent in the wiping-off property (e.g., fingerprint wiping-off property) of dirt, that is, antifouling property, is demanded.

As a result of studies, the present inventors have found that the conventional antifouling film is insufficient in antifouling property and adhesion between the substrate of the antifouling film and the polymer layer constituting the surface (uneven structure) of the antifouling film is also insufficient. Further, it has been found that the conventional antifouling film is insufficient in abrasion resistance and reliability. For example, when the surface of the polymer layer (the surface of the uneven structure) is rubbed, the projections may stick to each other and not return to the original state (the projections do not stand after collapse), or the projections may be broken, and thus improvement of wear resistance is required. In addition, under a high temperature/high humidity environment, a constituent material of the polymer layer may bleed out (bleed out) to degrade optical characteristics, and thus improvement in reliability is required.

As described above, no method has been found for providing a conventional antifouling film with excellent antifouling properties, adhesion, abrasion resistance, and reliability. For example, patent documents 1 to 3 do not describe the adhesion and reliability, and there is room for improvement in the improvement of the antifouling property and the wear resistance.

The present invention has been made in view of the above-described situation, and an object thereof is to provide an antifouling film having excellent antifouling properties, adhesion, abrasion resistance, and reliability.

Means for solving the problems

The present inventors have conducted various studies on an antifouling film having excellent antifouling properties, adhesion, abrasion resistance and reliability, and as a result, have found a structure in which a polymerizable composition constituting a polymer layer of the antifouling film contains components for improving the properties at a predetermined ratio. The present invention was achieved by perfectly solving the above problems.

That is, one aspect of the present invention is an antifouling film comprising: a substrate; and a polymer layer which is disposed on the surface of the base material and has a concavo-convex structure having a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light on the surface, wherein the polymer layer is a cured product of a polymerizable composition containing, in terms of active ingredients, 15 to 40 wt% of hexafunctional or higher acrylic urethane, 35 to 60 wt% of tetrafunctional or higher polyfunctional acrylate having 3 to 15 ethylene oxide groups per functional group, 15 to 30 wt% of monofunctional acrylate having no ethylene oxide group, 0.5 to 10 wt% of a fluorine-based release agent having a perfluoropolyether group and having a fluorine atom concentration of 50 wt% or less, and 0.5 to 5 wt% of a polymerization initiator.

The coefficient of dynamic friction of the surface of the polymer layer may be 2.0 or less.

The surface of the polymer layer may have a contact angle with water of 130 ° or more and a contact angle with hexadecane of 30 ° or more.

The monofunctional acrylate may also include at least one of N-acryloyl morpholine and N, N-dimethylacrylamide.

The thickness of the polymer layer may be 5.0 μm or more and 20.0 μm or less.

The average pitch of the plurality of projections may be 100nm or more and 400nm or less.

The average height of the plurality of projections may be 50nm or more and 600nm or less.

The average aspect ratio of the plurality of projections may be 0.8 or more and 1.5 or less.

Effects of the invention

According to the present invention, an antifouling film having excellent antifouling properties, adhesion, abrasion resistance and reliability can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view showing an antifouling film according to an embodiment.

Fig. 2 is a schematic perspective view illustrating the polymer layer of fig. 1.

Fig. 3 is a schematic cross-sectional view for explaining a method for producing an antifouling film according to an embodiment.

Detailed Description

The present invention will be described in more detail below with reference to the accompanying drawings, which illustrate embodiments of the present invention. Further, the respective configurations of the embodiments may be appropriately combined or changed within a range not departing from the gist of the present invention.

In the present specification, "X to Y" means "X or more and Y or less".

[ embodiment ]

The antifouling film according to the embodiment will be described below with reference to fig. 1 and 2. Fig. 1 is a schematic cross-sectional view showing an antifouling film according to an embodiment. Fig. 2 is a schematic perspective view illustrating the polymer layer of fig. 1.

The antifouling film 1 includes a base material 2 and a polymer layer 3 disposed on the surface of the base material 2.

Examples of the material of the substrate 2 include resins such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), and Methyl Methacrylate (MMA). In addition to the above materials, the base material 2 may also contain additives such as plasticizers. The surface of the substrate 2 (the surface on the polymer layer 3 side) may be subjected to an easy-adhesion treatment, and for example, a triacetyl cellulose film subjected to an easy-adhesion treatment can be used. The surface of the substrate 2 (the surface on the polymer layer 3 side) may be subjected to saponification treatment, and for example, a saponified triacetyl cellulose film may be used. When the antifouling film 1 is mounted on a display device such as a liquid crystal display device provided with a polarizing plate, the substrate 2 may constitute a part of the polarizing plate.

The thickness of the base material 2 is preferably 50 μm or more and 100 μm or less from the viewpoint of ensuring transparency and processability.

The polymer layer 3 has an uneven structure in which a plurality of convex portions (protrusions) 4 are provided on the surface at a pitch P (distance between apexes of adjacent convex portions 4) of the wavelength (780nm) of visible light, that is, a moth-eye structure (moth-eye structure). Therefore, the stain-resistant film 1 can exhibit excellent antireflection properties (low reflectance) due to the moth-eye structure.

The thickness T of the polymer layer 3 is preferably small from the viewpoint of aligning fluorine atoms in a fluorine-based release agent (described later) at a high concentration on the surface of the polymer layer 3 (the surface on the opposite side from the substrate 2). Specifically, the thickness T of the polymer layer 3 is preferably 5.0 μm or more and 20.0 μm or less, and more preferably 8.0 μm or more and 12.0 μm or less. As shown in fig. 1, the thickness T of the polymer layer 3 is a distance from the surface on the base material 2 side to the apex of the projection 4.

Examples of the shape of the projection 4 include: a shape (tapered shape) tapered toward the tip, such as a shape (bell shape) composed of a columnar lower portion and a hemispherical upper portion, and a tapered shape (tapered shape, conical shape). In fig. 1, the bottom side of the gap between adjacent convex portions 4 is inclined, but may be horizontal without being inclined.

From the viewpoint of sufficiently preventing the occurrence of optical phenomena such as moire and rainbow unevenness, the average pitch of the plurality of projections 4 is preferably 100nm or more and 400nm or less, and more preferably 100nm or more and 200nm or less. Specifically, the average pitch of the plurality of projections 4 is an average value of pitches of all adjacent projections in a region of 1 μm square in a plan photograph taken by a scanning electron microscope.

From the viewpoint of satisfying a preferable average aspect ratio of the plurality of projections 4 described later, the average height of the plurality of projections 4 is preferably 50nm or more and 600nm or less, and more preferably 100nm or more and 300nm or less. Specifically, the average height of the plurality of protrusions 4 is an average height of 10 protrusions arranged in series in a cross-sectional photograph taken by a scanning electron microscope. However, when 10 convex portions are selected, convex portions having a portion with a defect or a deformation (a portion that is deformed when a measurement sample is prepared) are excluded.

The average aspect ratio of the plurality of projections 4 is preferably 0.8 or more and 1.5 or less, and more preferably 1.0 or more and 1.3 or less. When the average aspect ratio of the plurality of projections 4 is less than 0.8, the occurrence of optical phenomena such as moire and iris unevenness cannot be sufficiently prevented, and there is a fear that excellent antireflection properties cannot be obtained. When the average aspect ratio of the plurality of convex portions 4 is larger than 1.5, there is a concern that workability of the concave-convex structure is lowered to cause sticking (sticking), or a transfer state when the concave-convex structure is formed is deteriorated (mold 6 to be described later is clogged or entangled). The average aspect ratio of the plurality of projections 4 means a ratio (height/pitch) of an average height to an average pitch of the plurality of projections 4.

The convex portions 4 may be arranged randomly or regularly (periodically). Although the arrangement of the convex portions 4 may have periodicity, it is preferable that the arrangement of the convex portions 4 does not have periodicity (is random) as shown in fig. 2, in view of the advantage that unnecessary diffracted light due to the periodicity is not generated.

The polymer layer 3 is a cured product of a polymerizable composition. Examples of the polymer layer 3 include a cured product of an active energy ray-curable polymerizable composition and a cured product of a thermosetting polymerizable composition. Here, the active energy ray refers to ultraviolet ray, visible ray, infrared ray, plasma, or the like. The polymer layer 3 is preferably a cured product of an active energy ray-curable polymerizable composition, and more preferably a cured product of an ultraviolet ray-curable polymerizable composition.

The polymerizable composition contains, in terms of active ingredients, 15 to 40% by weight of hexafunctional or higher acrylic urethane (hereinafter also referred to as component A), 35 to 60% by weight of tetrafunctional or higher polyfunctional acrylate containing 3 to 15 ethylene oxide groups per functional group (hereinafter also referred to as component B), 15 to 30% by weight of monofunctional acrylate having no ethylene oxide group (hereinafter also referred to as component C), 0.5 to 10% by weight of a fluorine-based release agent having a perfluoropolyether group and having a fluorine atom concentration of 50% by weight or lower (hereinafter also referred to as component D), and 0.5 to 5% by weight of a polymerization initiator (hereinafter also referred to as component E).

The active ingredient (active ingredient of the components a to E) of the polymerizable composition means a component which becomes a structural component of the polymer layer 3 after curing, and a component (for example, a solvent) which does not participate in the curing reaction (polymerization reaction) is excluded. For example, the active ingredient of the component D is a compound having a fluorine atom in the molecule.

The polymerizable composition may contain other components as long as the components a to E are contained in the above-mentioned ratio.

The components A to E will be described below.

(component A)

According to the component a, the crosslinking density of the polymer layer 3 is increased by the cohesive force of the urethane bond, and the abrasion resistance is improved by imparting appropriate hardness (elasticity). Further, the adhesiveness between the base material 2 and the polymer layer 3 (hereinafter, also simply referred to as adhesiveness) is improved by the cohesive force of the urethane bond.

In the component A, the number of functional groups of the acrylic urethane is 6 or more, preferably 8 or more, and more preferably 10 or more. When the number of functional groups of the urethane acrylate is 5 or less, the crosslinking density of the polymer layer 3 is not increased, the hardness becomes too low, and the abrasion resistance is lowered. On the other hand, if the number of functional groups of the urethane acrylate is too large, the viscosity of the urethane acrylate becomes too high, and the compatibility with other components is lowered, so that there is a concern that the abrasion resistance is lowered. From this viewpoint, a preferable upper limit value of the number of functional groups of the acrylic urethane is 15. Here, the number of functional groups of the urethane acrylate refers to the number of acryloyl groups per molecule.

The content of the component a in the polymerizable composition is 15 to 40 wt%, preferably 20 to 35 wt%, and more preferably 25 to 30 wt% in terms of the active ingredient. When the content of the component a is less than 15% by weight in terms of the active ingredient, the crosslinking density of the polymer layer 3 is not increased, and the hardness becomes too low, so that the abrasion resistance is lowered. Further, the amount of urethane bonds becomes too small, and thus the adhesiveness is lowered. When the content of the component a is more than 40% by weight in terms of the active ingredient, the crosslinking density of the polymer layer 3 becomes too high, and the elasticity thereof becomes insufficient (flexibility is reduced), and thus the abrasion resistance is reduced. When the polymerizable composition contains a plurality of components a, the total content of the plurality of components a may be within the above range in terms of the effective component.

Known examples of the component A include: urethane acrylate components (number of functional groups: 6) in "UA-306H", "UA-306T", "UA-306I" and "UA-510H" manufactured by Kyoeisha chemical Co., Ltd.; "KUA-9N" (number of functional groups: 9), "KUA-10N" (number of functional groups: 10), "KUA-15N" (number of functional groups: 15) manufactured by KSM company; "U-6 LPA", "UA-1100H" (number of functional groups: 6), "UA-33H" (number of functional groups: 9), "U-10 HA", "U-10 PA" (number of functional groups: 10), "UA-53H" (number of functional groups: 15) manufactured by New Miura chemical industries; "EBECRYL (registered trademark) 1290", "EBECRYL 5129" (functional group number: 6), "KRM (registered trademark) 8904" (functional group number: 9), "KRM 8452" (functional group number: 10) and the like manufactured by Daicel-Allnex corporation.

(component B)

According to the component B, the crosslinking density of the polymer layer 3 is increased, and the abrasion resistance is improved by imparting appropriate hardness (elasticity). Further, the high polarity of the ethylene oxide group improves the interaction with the base material 2, thereby improving the adhesion. It is considered that the abrasion resistance is related to the crosslinking density and the glass transition temperature of the polymer layer 3, and if the crosslinking density is increased and the glass transition temperature is decreased, the abrasion resistance can be remarkably improved. For example, when the polymerizable composition contains a polyfunctional acrylate having a propylene oxide group, the glass transition temperature becomes higher than that in the case where the polymerizable composition contains a polyfunctional acrylate having an ethylene oxide group. The reason for this is that the molecules transportbranched-CH possessed by causal epoxypropyl group₃But is restrained. Furthermore, a propylene oxide group (hydrocarbon group as well) is less polar than an ethylene oxide group, and interaction with the substrate 2 is reduced, thereby reducing adhesion. Therefore, in the present embodiment, the ethylene oxide group is selected from the viewpoint of abrasion resistance and adhesion.

In the component B, the number of functional groups of the polyfunctional acrylate is 4 or more, preferably 6 or more, and more preferably 9 or more. When the number of functional groups of the multifunctional acrylate is 3 or less, the crosslinking density of the polymer layer 3 is not increased, the hardness becomes too low, and the abrasion resistance is lowered. On the other hand, if the number of functional groups of the multifunctional acrylate is too large, the crosslinking density of the polymer layer 3 becomes too high, and the elasticity thereof is insufficient, so that there is a fear that the abrasion resistance is lowered. From this viewpoint, the preferable upper limit value of the number of functional groups of the multifunctional acrylate is 15. Here, the number of functional groups of the multifunctional acrylate refers to the number of acryloyl groups per molecule.

In the component B, the number of the oxirane groups is 3 to 15 per functional group, preferably 4 to 12 per functional group, and more preferably 6 to 9 per functional group. When the number of ethylene oxide groups is less than 3 per functional group, the elasticity of the polymer layer 3 is insufficient, and thus the abrasion resistance is lowered. When the number of ethylene oxide groups is more than 15 per functional group, the crosslinking density of the polymer layer 3 becomes too low, and thus the abrasion resistance is lowered. Here, the number of ethylene oxide groups per functional group means (number of ethylene oxide groups per molecule)/(number of acryl groups per molecule).

The content of the component B in the polymerizable composition is 35 to 60 wt%, preferably 40 to 55 wt%, and more preferably 45 to 50 wt% in terms of the active ingredient. When the content of the component B is less than 35% by weight in terms of the effective component, the elasticity of the polymer layer 3 is insufficient, and thus the abrasion resistance is lowered. When the content of the component B is more than 60% by weight in terms of the effective component, the crosslinking density of the polymer layer 3 becomes too low, and thus the abrasion resistance is lowered. When the polymerizable composition contains a plurality of components B, the total content of the plurality of components B may be in the range as described above in terms of the effective component.

Examples of the component B include ethoxylated pentaerythritol tetraacrylate and ethoxylated polyglycerol polyacrylate. As a well-known example of the ethoxylated pentaerythritol tetraacrylate, "ATM-35E" (number of functional groups: 4, number of ethylene oxide groups: 8.75 per functional group) manufactured by New Miura chemical industries, etc. can be given. Known examples of ethoxylated polyglycerol polyacrylates include: "NK ECONOMER (registered trademark) A-PG 5027E" (number of functional groups: 9, number of ethylene oxide groups: 3 per functional group), "NK ECONOMER A-PG 5054E" (number of functional groups: 9, number of ethylene oxide groups: 6 per functional group) manufactured by Xinzhongcun chemical industries, and the like.

(component C)

According to the component C, the compatibility of the component A, the component B and the component D is improved, and therefore, the abrasion resistance is improved. Further, the curing shrinkage of the polymerizable composition is suppressed, and the cohesive force with the base material 2 is improved, thereby improving the adhesion. Since the components a and B have large molecular weights, they have low compatibility with each other, and since they are polyfunctional, they have low adhesion due to curing shrinkage. Further, the component D may have a long-chain structure and may have low compatibility with the components A and B. Therefore, the component C not only acts to improve the cohesion with the base material 2, but also acts as a reactive diluent (co-solvent) for the components a, B, and D.

The component C does not contain ethylene oxide groups. The monofunctional acrylate having an oxirane group has a low reactivity, and tends to bleed out when contained in a large amount, although the glass transition temperature is lowered due to its long-chain structure. Further, the monofunctional acrylate having an ethylene oxide group has low compatibility with the component D, and therefore, the compatibility cannot be improved when the amount is small, and the compatibility is improved but easily bleeds out when the amount is large. Such problems similarly occur, for example, with a monomer having a propylene oxide group, a monomer having a long-chain hydrocarbon group, and the like.

The content of the component C in the polymerizable composition is 15 to 30 wt%, preferably 18 to 28 wt%, and more preferably 20 to 25 wt% in terms of the active ingredient. When the content of the component C is less than 15% by weight in terms of the active ingredient, the lubricity is lowered, and as a result, the wear resistance is lowered. Further, curing shrinkage of the polymerizable composition is not suppressed, and the adhesiveness is lowered. When the content of the component C is more than 30% by weight in terms of the effective component, the crosslinking density of the polymer layer 3 becomes too low, and thus the abrasion resistance is lowered. When the polymerizable composition contains a plurality of components C, the total content of the plurality of components C may be in the range as described above in terms of the effective component.

Examples of the component C include: amide group-containing monomers such as N-acryloylmorpholine, N-dimethylacrylamide, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, diacetone acrylamide and N-N-butoxymethylacrylamide; ether group-containing monomers such as tetrahydrofuran acrylate; hydroxyl group-containing monomers such as 4-hydroxybutyl acrylate and the like. Examples of N-acryloylmorpholine include "ACMO (registered trademark)" manufactured by KJ Chemicals, Inc. Examples of N, N-dimethylacrylamide are known, and "DMAA (registered trademark)" manufactured by KJ Chemicals. Examples of N, N-diethylacrylamide are known as "DEAA (registered trademark)" manufactured by KJ Chemicals, Inc. Examples of known N- (2-hydroxyethyl) acrylamide include "HEAA (registered trademark)" manufactured by KJ Chemicals. Examples of diacetone acrylamide include "DAAM (registered trademark)" manufactured by japan chemical company. Examples of N-N-butoxymethylacrylamide which is known include "NBMA" manufactured by MRC Unitec Co. Examples of the tetrahydrofuran acrylate are known as "Biscoat # 150" manufactured by osaka organic chemical industry corporation. Examples of the known 4-hydroxybutyl acrylate include "4 HBA" manufactured by Nippon chemical Co., Ltd.

Component C preferably contains at least one of N-acryloyl morpholine and N, N-dimethylacrylamide. With this structure, the viscosity of the component C is reduced, and the compatibility with the components a, B, and D is further improved. Further, when the substrate 2 is a triacetyl cellulose film, the adhesiveness is further improved.

(component D)

According to the component D, fluorine atoms are uniformly aligned on the surface of the polymer layer 3 (the surface opposite to the base material 2), and the surface free energy of the polymer layer 3 is reduced, thereby improving the antifouling property. Further, the smoothness is improved, and as a result, the wear resistance is improved.

The component D has a fluorine atom concentration of 50 wt% or less. When the fluorine atom concentration is higher than 50% by weight, the compatibility with the components a to C becomes too low, and the fluorine atoms are not uniformly aligned on the surface of the polymer layer 3 (the surface on the opposite side to the base material 2), and thus the stain-proofing property and the abrasion resistance are lowered. Moreover, the film is likely to bleed out under high temperature/high humidity environment, and reliability is lowered. On the other hand, if the fluorine atom concentration is too low, the amount of fluorine atoms aligned on the surface of the polymer layer 3 (the surface opposite to the base material 2) becomes too small, and there is a concern that the stain-proofing property and the abrasion resistance are lowered. From this viewpoint, the lower limit of the fluorine atom concentration is preferably 20% by weight.

The component D contains a perfluoropolyether group. The stain-proofing property and abrasion resistance of the polymer layer 3 are not sufficiently improved by a release agent having no perfluoropolyether group (for example, a fluorine-based release agent having a perfluoroalkyl group, a silicon-based release agent, and the like).

The content of the component D in the polymerizable composition is 0.5 to 10% by weight, preferably 1 to 5% by weight, and more preferably 1.5 to 3% by weight in terms of the active ingredient. When the content of the component D is less than 0.5 wt% in terms of active ingredient, the amount of fluorine atoms aligned on the surface of the polymer layer 3 (the surface opposite to the substrate 2) is too small, and the antifouling property is lowered. Further, the lubricity is lowered, and as a result, the wear resistance is lowered. When the content of the component D is more than 10% by weight in terms of the active ingredient, the compatibility with the components a to C becomes too low, and fluorine atoms are not uniformly aligned on the surface of the polymer layer 3 (the surface opposite to the base material 2), and thus the stain-proofing property and the abrasion resistance are lowered. Moreover, the film is likely to bleed out under high temperature/high humidity environment, and reliability is lowered. When the polymerizable composition contains a plurality of components D, the total content of the plurality of components D may be in the range as described above in terms of the effective component.

Known examples of the component D include Fomblin (registered trademark) MT70 (fluorine atom concentration: 43 wt%) and Fomblin AD1700 (fluorine atom concentration: 24 wt%) manufactured by Solvay.

(component E)

According to the component E, the curing properties of the polymerizable composition are improved.

The content of the component E in the polymerizable composition is 0.5 to 5% by weight, preferably 1 to 4% by weight, and more preferably 1.5 to 3% by weight in terms of the active ingredient. When the content of the component E is less than 0.5% by weight in terms of the active ingredient, insufficient curing of the polymerizable composition occurs. If the content of the component E is more than 5% by weight in terms of the active ingredient, the component E is likely to bleed out under a high-temperature/high-humidity environment, and the reliability is lowered. When the polymerizable composition contains a plurality of components E, the total content of the plurality of components E may be in the range as described above in terms of the effective component.

Examples of the component E include a photopolymerization initiator and a thermal polymerization initiator. The component E is preferably a photopolymerization initiator. The photopolymerization initiator is active against active energy rays and is added to initiate a polymerization reaction for polymerizing monomers.

Examples of the photopolymerization initiator include a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator. Examples of such photopolymerization initiators include: acetophenones such as p-tert-butyl trichloroacetophenone, 2' -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like; ketones such as benzophenone, 4' -bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone and 2-isopropylthioxanthone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like; benzil ketals such as benzil dimethyl ketal and hydroxycyclohexyl phenyl ketone; acylphosphine oxides such as 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; and alkylbenzophenones such as 1-hydroxy-cyclohexyl-phenyl-ketone. Examples of known 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide include "LUCIRIN (registered trademark) TPO" and "IRGACURE (registered trademark) TPO" manufactured by BASF corporation. Examples of the bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide include "IRGACURE 819" manufactured by BASF corporation. Examples of the known 1-hydroxy-cyclohexyl-phenyl-ketone include "IRGACURE 184" manufactured by BASF corporation.

The polymerizable composition may further contain a solvent (a component other than the active ingredient). In this case, the solvent may be contained in the components a to E together with the active ingredient, or may be contained separately from the components a to E.

Examples of the solvent include: alcohols (having 1 to 10 carbon atoms such as methanol, ethanol, n-propanol or isopropanol, n-butanol, sec-butanol or tert-butanol, benzyl alcohol, octanol and the like), ketones (having 3 to 8 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone and the like), esters or ether esters (having 4 to 10 carbon atoms such as ethyl acetate, butyl acetate, ethyl lactate and the like), γ -butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, ethers (having 4 to 10 carbon atoms such as EG (ethylene glycol) monomethyl ether (methyl cellosolve), EG monoethyl ether (ethyl cellosolve), diethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether and the like), aromatic hydrocarbons (having 6 to 10 carbon atoms such as benzene, toluene, xylene and the like), amides (having 3 to 10 carbon atoms such as dimethylformamide, dimethylacetamide, octanol and the like), amides, N-methylpyrrolidone, etc.), halogenated hydrocarbons (carbon number 1 to 2: for example, methylene chloride, ethylene dichloride, etc.), petroleum solvents (for example, petroleum ether, naphtha, etc.), and the like.

As described above, according to the present embodiment, the antifouling film 1 having excellent antifouling property, adhesion property, abrasion resistance, and reliability can be realized.

From the viewpoint of stain resistance, it is preferable that the surface of the polymer layer 3 (the surface on the opposite side to the base material 2) has a contact angle of water of 130 ° or more and a contact angle of hexadecane of 30 ° or more.

From the viewpoint of abrasion resistance, the coefficient of dynamic friction of the surface (the surface on the opposite side to the base material 2) of the polymer layer 3 is preferably 2.0 or less, more preferably 1.5 or less, and still more preferably 1.0 or less.

The application of the antifouling film 1 is not particularly limited as long as the excellent antifouling property is flexibly utilized, and for example, the application may be an optical film such as an antireflection film. Such an antireflection film contributes to improvement of visibility by being mounted inside or outside the display device.

The antifouling property of the antifouling film 1 may mean that the dirt attached to the surface of the polymer layer 3 (the surface opposite to the base material 2) can be easily removed, or that the dirt is not easily attached to the surface of the polymer layer 3 (the surface opposite to the base material 2).

The antifouling film 1 is produced by the following production method, for example. Fig. 3 is a schematic cross-sectional view for explaining a method for producing an antifouling film according to an embodiment.

(Process (1): application of polymerizable composition)

As shown in fig. 3(a), the polymerizable composition 5 is applied to the surface of the base material 2.

Examples of the method for applying the polymerizable composition 5 include a method of applying the composition by a spray method, a gravure method, a slit die method, a bar coating method, and the like. As a method for applying the polymerizable composition 5, coating by a gravure method or a slit die method is preferable from the viewpoint of making the film thickness uniform and improving productivity.

The polymerizable composition 5 contains the components a to E in the above-mentioned proportions. Here, when the polymerizable composition 5 further contains a solvent (a component other than the active ingredient), the polymerizable composition 5 may be applied and then subjected to a heat treatment (drying treatment) for removing the solvent. The heat treatment is preferably performed at a temperature of the boiling point of the solvent or higher.

(Process (2): formation of concave-convex Structure)

As shown in fig. 3(b), the base material 2 is pressed against the mold 6 with the polymerizable composition 5 interposed therebetween. As a result, an uneven structure is formed on the surface (the surface on the opposite side to the substrate 2) of the polymerizable composition 5.

(Process (3): curing of the polymerizable composition)

The polymerizable composition 5 having the uneven structure on the surface is cured. As a result, the polymer layer 3 is formed as shown in fig. 3 (c).

Examples of the method for curing the polymerizable composition 5 include irradiation with active energy rays, heating, and the like. The curing of the polymerizable composition 5 is preferably performed by irradiation with active energy rays, and more preferably by irradiation with ultraviolet rays. The irradiation with the active energy ray may be performed from the side of the base material 2 of the polymerizable composition 5, or may be performed from the side of the mold 6 of the polymerizable composition 5. The number of irradiation with active energy rays of the polymerizable composition 5 may be only 1 time, or may be plural times. The curing of the polymerizable composition 5 (the process (3)) may be performed at the same timing as the formation of the uneven structure of the polymerizable composition 5 (the process (2)).

(Process (4): mold stripping)

As shown in fig. 3(d), the mold 6 is peeled off from the polymer layer 3. As a result, the antifouling film 1 was completed.

In the above-described manufacturing process, if the substrate 2 is rolled, for example, the processes (1) to (4) can be continuously and efficiently performed.

As the mold 6, for example, a mold manufactured by the following method can be used. First, aluminum, which is a material of the mold 6, is formed on the surface of the support base by sputtering. Then, by alternately repeating anodization and etching with respect to the formed aluminum layer, a master model (mold 6) having a moth-eye structure can be produced. At this time, the time for performing the anodic oxidation and the time for performing the etching are adjusted, whereby the uneven structure of the mold 6 can be changed.

Examples of the material of the supporting base include: glass; metals such as stainless steel and nickel; polyolefin resins such as polypropylene, polymethylpentene, and cyclic olefin polymers (typically, "Zeonor (registered trademark)" manufactured by Zeon corporation of japan as norbornene resins, and "Arton (registered trademark)" manufactured by JSR corporation); a polycarbonate resin; resins such as polyethylene terephthalate, polyethylene naphthalate and triacetyl cellulose. Instead of an article obtained by forming aluminum on the surface of a support base, an aluminum base may be used.

Examples of the shape of the mold 6 include a flat plate shape and a roll shape.

The surface of the mold 6 is preferably subjected to a mold release treatment. This enables the mold 6 to be easily peeled off from the polymer layer 3. Further, since the surface free energy of the mold 6 is low, in the above-mentioned process (2), when the substrate 2 is pressed against the mold 6, the fluorine atoms in the component D can be uniformly aligned on the surface of the polymerizable composition 5 (the surface opposite to the substrate 2). Further, the fluorine atoms in the component D can be prevented from being released from the surface (the surface opposite to the substrate 2) of the polymerizable composition 5 before the polymerizable composition 5 is cured. As a result, in the antifouling film 1, the fluorine atoms in the component D can be uniformly aligned on the surface of the polymer layer 3 (the surface on the opposite side to the substrate 2).

Examples of the material used for the mold release treatment of the mold 6 include a fluorine-based material, a silicon-based material, and a phosphate-based material. Examples of the fluorine-based material include "Optools (registered trademark) DSX" manufactured by the major industries, and "Optools AES 4" manufactured by the major industries.

[ examples and comparative examples ]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

In examples and comparative examples, materials used for producing antifouling films were as follows.

(substrate)

"TAC-TD 80U" manufactured by Fuji film corporation was used, and its thickness was 80 μm.

(polymerizable composition)

The polymerizable compositions R1 to R38 having the compositions shown in tables 1 to 13 were used. The names of the respective components of the polymerizable composition are abbreviated as follows.

< urethane acrylate >)

·“A1”

"UA-306H" manufactured by Kyoeisha chemical Co., Ltd "

Number of functional groups: 6

Urethane acrylate component (active ingredient): 70% by weight

Multifunctional acrylate component (active ingredient): 30% by weight

·“A2”

"KUA-9N" manufactured by KSM corporation "

Number of functional groups: 9

The effective components are as follows: 100% by weight

·“A3”

"KUA-10N" manufactured by KSM corporation "

Number of functional groups: 10

The effective components are as follows: 100% by weight

·“A4”

"KUA-15N" manufactured by KSM corporation "

Number of functional groups: 15

The effective components are as follows: 100% by weight

·“A5”

"EBECRYL 4858" manufactured by Daicel-Allnex corporation "

Number of functional groups: 2

The effective components are as follows: 100% by weight

·“A6”

"EBECRYL 8465" manufactured by Daicel-Allnex corporation "

Number of functional groups: 3

The effective components are as follows: 100% by weight

·“A7”

"EBECRYL 8210" manufactured by Daicel-Allnex corporation "

Number of functional groups: 4

The effective components are as follows: 100% by weight

< multifunctional acrylates >

·“B1”

"ATM-35E" manufactured by New Zhongcun chemical industries "

Number of functional groups: 4

Number of ethylene oxide groups: 8.75 per functional group

The effective components are as follows: 100% by weight

·“B2”

"NK ECONOMER A-PG 5027E" manufactured by NENGZHONGvillage chemical industry Co., Ltd "

Number of functional groups: 9

Number of ethylene oxide groups: 3 per functional group

The effective components are as follows: 100% by weight

·“B3”

"NK ECONOMER A-PG 5054E" manufactured by Xinzhongcun chemical industries "

Number of functional groups: 9

Number of ethylene oxide groups: 6 per functional group

The effective components are as follows: 100% by weight

·“B4”

"A-600" manufactured by New Zhongcun chemical industries "

Number of functional groups: 2

Number of ethylene oxide groups: 7 per functional group

The effective components are as follows: 100% by weight

·“B5”

"A-TMPT-9 EO" manufactured by Xinzhongcun chemical industries "

Number of functional groups: 3

Number of ethylene oxide groups: 3 per functional group

The effective components are as follows: 100% by weight

·“B6”

"AT-30E" manufactured by Xinzhongcun chemical industry Co., Ltd "

Number of functional groups: 3

Number of ethylene oxide groups: 10 per functional group

The effective components are as follows: 100% by weight

·“B7”

"KAYARAD (registered trademark) DPEA-12" manufactured by Japan chemical Co., Ltd "

Number of functional groups: 6

Number of ethylene oxide groups: 2 per functional group

The effective components are as follows: 100% by weight

< monofunctional acrylate >)

·“C1”

Biscoat #150 manufactured by Osaka organic chemical industries, Ltd "

Ethylene oxide group: does not have

The effective components are as follows: 100% by weight

·“C2”

"ACMO" manufactured by KJ Chemicals "

Ethylene oxide group: does not have

The effective components are as follows: 100% by weight

·“C3”

"DMAA" manufactured by KJ Chemicals "

Ethylene oxide group: does not have

The effective components are as follows: 100% by weight

·“C4”

"AM-90G" manufactured by Xinzhongcun chemical industry Co., Ltd "

Ethylene oxide group: has the advantages of

The effective components are as follows: 100% by weight

< Release agent >

·“D1”

"Fomblin MT 70" manufactured by Solvay "

Perfluoropolyether group: has the advantages of

Fluorine atom concentration: 43% by weight

The effective components are as follows: 80% by weight

·“D2”

"Fomblin AD 1700" manufactured by Solvay Corp "

Perfluoropolyether group: has the advantages of

Fluorine atom concentration: 24% by weight

The effective components are as follows: 70% by weight

·“D3”

"Fomblin MD 700" manufactured by Solvay "

Perfluoropolyether group: has the advantages of

Fluorine atom concentration: 52% by weight

The effective components are as follows: 100% by weight

·“D4”

"BYK (registered trademark) -UV 3575" manufactured by BYK Chemie Japan K.K "

Perfluoropolyether group: does not have (silicon series release agent)

The effective components are as follows: 50% by weight

·“D5”

"X-22-2445" manufactured by shin-Etsu chemical industries, Inc "

Perfluoropolyether group: does not have (silicon series release agent)

The effective components are as follows: 100% by weight

·“D6”

"TEGO (registered trademark) Rad 2700" manufactured by Evonic corporation "

Perfluoropolyether group: does not have (silicon series release agent)

The effective components are as follows: 100% by weight

·“D7”

"FM-0711" manufactured by JNC corporation "

Perfluoropolyether group: does not have (silicon series release agent)

The effective components are as follows: 100% by weight

·“D8”

"CHEMINOX (registered trademark) FAAC-6" manufactured by Unimatec corporation "

Perfluoropolyether group: does not have (has a perfluoroalkyl group)

The effective components are as follows: 100% by weight

·“D9”

"Ftergent (registered trademark) 601 AD" manufactured by Neos corporation "

Perfluoropolyether group: does not have (has a perfluoroalkyl group)

The effective components are as follows: 25% by weight

·“D10”

"Megaface (registered trademark) RS-76-NS" manufactured by DIC corporation "

Perfluoropolyether group: does not have (has a perfluoroalkyl group)

The effective components are as follows: 20% by weight

< polymerization initiator >

·“E1”

"LUCIRIN TPO" manufactured by BASF corporation "

The effective components are as follows: 100% by weight

The "effective component ratio" in tables 1 to 13 represents a ratio obtained by converting the content of each component (such as urethane acrylate) in the polymerizable composition into an effective component, that is, a content (unit: weight%) of the effective component of each component with respect to 100% by weight of the total amount of the effective components in the polymerizable composition. In addition, in the polymerizable composition R2, the content of the polyfunctional acrylate (classified: other) not corresponding to the component B was 8.1% by weight in terms of the effective component, but this was the ratio of the effective component of the polyfunctional acrylate component contained in the acrylic urethane A1. In addition, in the polymerizable composition R19, the content of the polyfunctional acrylate (classified: other) not corresponding to the component B was 5.4% by weight in terms of the effective component, which is the ratio of the effective component of the polyfunctional acrylate component contained in the acrylic urethane A1.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

[ Table 13]

(mold)

A mold produced by the following method was used. First, aluminum, which is a material of a mold, was formed on a 10cm square glass substrate by a sputtering method. The thickness of the aluminum layer formed was 1.0. mu.m. Next, anodization and etching are alternately repeated for the formed aluminum layer, thereby forming an anodized layer in which a plurality of fine holes (the distance between the bottom points of adjacent holes (recesses) is equal to or less than the wavelength of visible light) are formed. Specifically, anodization, etching, anodization (5 times, 4 times), etching, and anodization (anodization) were performed in this order to form minute holes (recesses) having a tapered shape (tapered shape) that tapered toward the inside of the aluminum layer, and as a result, a mold having an uneven structure was obtained. The anodic oxidation was carried out using oxalic acid (concentration: 0.03 wt%) under conditions of a liquid temperature of 5 ℃ and an applied voltage of 80V. The time for 1 anodization was 25 seconds. The etching was carried out at a liquid temperature of 30 ℃ using phosphoric acid (concentration: 1 mol/l). The time for 1 etching was set to 25 minutes. The mold was observed with a scanning electron microscope, and the depth of the concave portion was 290 nm. Further, the surface of the mold was subjected to mold release treatment in advance by "Optools AES 4" manufactured by the dajin industries.

(example 1)

The antifouling film of example 1 was produced by the following production method.

(Process (1): application of polymerizable composition)

The polymerizable composition R1 was dropped (coated) in a band shape onto the surface of the base material 2. Then, the polymerizable composition R1 was spread over the entire surface of the base material 2 using a bar coater. Then, the article having the polymerizable composition R1 coated on the surface of the base material 2 was put into an oven and subjected to a heat treatment at a temperature of 80 ℃ for 1 minute to volatilize the solvent from the polymerizable composition R1.

(Process (2): formation of concave-convex Structure)

The substrate 2 was pressed against the mold 6 by a hand roller with the polymerizable composition R1 (after the solvent was evaporated) sandwiched therebetween. As a result, an uneven structure was formed on the surface (the surface opposite to the substrate 2) of the polymerizable composition R1.

(Process (3): curing of the polymerizable composition)

The polymerizable composition R1 having an uneven structure on the surface was irradiated with ultraviolet light from the substrate 2 side (irradiation dose: 200 mJ/cm)²) And hardening is performed. As a result, the polymer layer 3 is formed.

(Process (4): mold stripping)

The mould 6 is peeled off the polymer layer 3. As a result, the antifouling film 1 was completed. The thickness T of the polymer layer 3 was 9.8 μm.

The surface specification of the antifouling film 1 is as follows.

Shape of the convex portion 4: average pitch of the bell-shaped protrusions 4: 200nm

Average height of convex portion 4: 200nm

Average aspect ratio of convex portion 4: 1.0

The surface specification of the antifouling film 1 was evaluated by using a scanning electron microscope "S-4700" manufactured by hitachi High-Technologies. In addition, in the evaluation, osmium oxide VIII (thickness: 5nm) manufactured by Wavefosis was applied to the surface of the polymer layer 3 (the surface opposite to the substrate 2) using an osmium applicator "Neoc-ST" manufactured by Meiwafosis.

(examples 2 to 15 and comparative examples 1 to 23)

Antifouling films of the respective examples were produced in the same manner as in example 1, except that the compositions shown in tables 14 to 21 were changed.

[ evaluation ]

The following evaluations were performed on the antifouling films of the respective examples. The results are shown in tables 14 to 21.

(transparency of the polymerizable composition)

The polymerizable compositions used in the respective examples (in a state before heat treatment) were placed in a transparent test tube, and the state was visually observed under an environment of an illuminance of 100lx (fluorescent lamp). The criteria for determination are as follows.

O: transparent or very slightly cloudy.

And (delta): slightly cloudy, but no precipitate was observed even after leaving for 1 day.

X: turbid white, and precipitates were visible after standing for 1 day.

Here, the higher the transparency of the polymerizable composition, the higher the compatibility of the release agent in the polymerizable composition is judged to be.

(antifouling Property)

As the stain-proofing property, water repellency, oil repellency, and fingerprint wipeability were evaluated.

As the water repellency, the contact angle of water to the surface of the antifouling film of each example was evaluated. Specifically, water was dropped on the surface (surface opposite to the base material) of the polymer layer of each antifouling film, and the contact angle immediately after the dropping was measured.

As oil repellency, the contact angle of hexadecane to the surface of the antifouling film of each example was evaluated. Specifically, hexadecane was dropped on the surface (surface opposite to the base material) of the polymer layer of each antifouling film, and the contact angle immediately after dropping was measured.

The contact angle is an average value of the contact angles at 3 points measured by θ/2 method (θ/2 ═ arctan (h/r), θ: contact angle, r: radius of droplet, h: height of droplet) using a hand-held contact angle meter "PCA-1" manufactured by synechia scientific corporation. Here, as the 1 st measurement point, the central portion of the antifouling film of each example was selected, and as the 2 nd and 3 rd measurement points, two points 20mm or more from the 1 st measurement point and at positions point-symmetrical to each other with respect to the 1 st measurement point were selected.

The fingerprint removability was evaluated by the following method. First, a black acrylic plate was attached to the surface of the base opposite to the polymer layer via an optical adhesive layer, with respect to the antifouling films of the examples. Then, after attaching fingerprints to the surface (surface opposite to the base material) of the polymer layer of each antifouling film, the surface was rubbed back and forth 10 times with "Bemcot (registered trademark) S-2" manufactured by asahi chemical fiber company, and whether or not the fingerprints were wiped off was visually observed under an environment of an illuminance of 100lx (fluorescent lamp). The criteria for determination are as follows.

O: the fingerprint is completely wiped off, and no wiping residue is seen.

And (delta): the fingerprint was not noticeable, but if reflected under a fluorescent lamp, the wiping residue was slightly visible.

X: the fingerprint is not erased at all.

Here, the case where the determination is "o" or "Δ" is determined as a tolerable level (excellent fingerprint wipeability).

(Tight-contact property)

The adhesion was evaluated by the following method. First, the surface of the polymer layer (the surface opposite to the base material) of the antifouling film of each example was cut into 11 vertical and 11 horizontal cuts at 1mm intervals in a checkered pattern by a dicing blade, and 100 square grids (1mm square) were drawn. Then, after a polyester tape "No. 31B" manufactured by the japanese east electrical company was pressure-bonded to the mesh portion, the tape was peeled off at a speed of 100mm/s in a direction of 90 ° with respect to the surface of the mesh portion. Then, the peeling state of the polymer layer on the base material was visually observed, and the number "M" (unit: number) of the remaining cells in which the polymer layer on the base material was not peeled was counted. The criteria for determination are as follows.

○：M＝100

△：M＝95～99

×：M＝0～94

Here, the case where the determination is "o" or "Δ" is determined as a tolerable level (excellent adhesion).

(abrasion resistance)

The abrasion resistance was evaluated by the smoothness and the steel wool resistance.

The dynamic friction coefficient of the surface of the antifouling film of each example was evaluated as smoothness. Specifically, the antifouling films of the respective examples were first fixed on a stage of a surface texture measuring machine "HEIDON (registered trademark) -14 FW" manufactured by new eastern science corporation, and the horizontal state was confirmed. Then, a probe was placed on the surface (surface opposite to the base material) of the polymer layer of the antifouling film of each example, and the surface was rubbed by 20mm while applying a load of 400 g. Then, a stable portion of the obtained graph (chart) is extracted, and the kinetic friction coefficient is calculated.

The steel wool resistance was evaluated by the following method. First, the surface of the polymer layer (surface opposite to the base material) of the antifouling film of each example was rubbed with a load of 400g applied to steel wool "# 0000" manufactured by nippon steel wool corporation. Then, the number of "N" (unit: bar) of scratches formed on the surface of the polymer layer (surface opposite to the base material) of the antifouling films of the respective examples was counted by visual observation under an illumination of 100lx (fluorescent lamp). Further, in the case of rubbing with steel wool, a surface texture measuring machine "HEIDON-14 FW" manufactured by Neweastern science, as a testing machine, was used, and a stroke width was 30mm, a speed was 100mm/s, and the number of times of rubbing was 10 times. The criteria for determination are as follows.

◎：N＝0

○：N＝1～3

△：N＝4～10

×：N＝11～20

××：N≧21

Here, the case of being judged as ∈,. smallcircle, or Δ is judged as an allowable level (excellent steel wool resistance).

(reliability)

As reliability, occurrence of bleeding out of the antifouling films of the respective examples was evaluated. Specifically, the antifouling films of the respective examples were subjected to a high temperature/high humidity test in which the films were left to stand at 60 ℃ and 95% humidity for 1000 hours. Then, the polymer layer of each antifouling film was visually observed for cloudiness under an illumination of 100lx (fluorescent lamp). As a result of visual observation, when the polymer layer was not clouded, it was judged that no bleeding occurred, and it was judged to be acceptable (OK). On the other hand, when the polymer layer is cloudy, it is determined that bleeding has occurred, and it is determined that the reliability is Not Good (NG). On the other hand, when it is difficult to determine by visual observation, the regular reflection spectra at 5 ° of incident light measured before and after the high temperature/high humidity test are superimposed, and the determination is made based on the presence or absence of a difference in the spectra between the two. Specifically, the reflectivities before and after the high temperature/high humidity test are compared, and a case where the both are not deviated is determined as "good reliability" (OK), and a case where the both are deviated (a case where the reflectance is totally increased after the high temperature/high humidity test) is determined as "bad reliability" (NG). The regular reflection spectrum at 5 ° of incident light was measured as follows. First, a black acrylic plate was attached to the surface of the base opposite to the polymer layer of the antifouling film of each example. Then, the surface of the polymer layer (the surface opposite to the base material) of each of the antifouling films of examples was irradiated with a light source from an azimuth of a polar angle of 5 °, and a regular reflection spectrum was measured in a wavelength region of 380nm to 780nm using "UV-3100 PC" manufactured by Shimadzu corporation.

[ Table 14]

[ Table 15]

[ Table 16]

[ Table 17]

[ Table 18]

[ Table 19]

[ Table 20]

[ Table 21]

As shown in tables 14 to 16, examples 1 to 15 all had excellent antifouling property, adhesion property, abrasion resistance and reliability. On the other hand, as shown in tables 17 to 21, comparative examples 1 to 23 all had low at least one of antifouling property, adhesion property, abrasion resistance and reliability.

In comparative example 1, the number of functional groups of the urethane acrylate a5 in the polymerizable composition R16 was less than 6, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 2, the number of functional groups of the urethane acrylate a6 in the polymerizable composition R17 was less than 6, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 3, the number of functional groups of the urethane acrylate a7 in the polymerizable composition R18 was less than 6, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 4, the content of the urethane acrylate component derived from urethane acrylate a1 in the polymerizable composition R19 was less than 15% by weight in terms of active ingredient, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 5, the polymerizable composition R20 had a low abrasion resistance (steel wool resistance) because the content of the urethane acrylate A3 was more than 40% by weight in terms of active ingredient and the content of the polyfunctional acrylate B3 was less than 35% by weight in terms of active ingredient.

In comparative example 6, the number of functional groups of the polyfunctional acrylate B4 in the polymerizable composition R21 was less than 4, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 7, the number of functional groups of the polyfunctional acrylate B5 in the polymerizable composition R22 was less than 4, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 8, the number of functional groups of the polyfunctional acrylate B6 in the polymerizable composition R23 was less than 4, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 9, the number of ethylene oxide groups in the polyfunctional acrylate B7 in the polymerizable composition R24 was less than 3 per functional group, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 10, the polymerizable composition R25 had a low abrasion resistance (steel wool resistance) because the content of the urethane acrylate A3 was less than 15 wt% in terms of active ingredient and the content of the polyfunctional acrylate B3 was more than 60 wt% in terms of active ingredient.

In comparative example 11, the monofunctional acrylate C4 in the polymerizable composition R26 had an ethylene oxide group, and therefore, the compatibility with other components was lowered, and the transparency of the polymerizable composition R26 was low. Further, antifouling property, adhesion property and abrasion resistance (steel wool resistance) are also low.

In comparative example 12, the content of the monofunctional acrylate C3 in the polymerizable composition R27 was less than 15% by weight in terms of active ingredient, and therefore, the adhesiveness was low.

In comparative example 13, the content of the monofunctional acrylate C3 in the polymerizable composition R28 was higher than 30% by weight in terms of active ingredient, and therefore, the abrasion resistance (steel wool resistance) was low.

In comparative example 14, since the fluorine atom concentration of the release agent D3 in the polymerizable composition R29 was higher than 50% by weight, the compatibility with other components was lowered, and the transparency of the polymerizable composition R29 was low. Further, antifouling property, abrasion resistance and reliability are low.

In comparative example 15, the polymerizable composition R30 contained no fluorine-based release agent (component D), and therefore had low stain resistance and abrasion resistance.

In comparative example 16, the content of the release agent D1 in the polymerizable composition R31 was more than 10% by weight in terms of active ingredient, and therefore, the abrasion resistance (steel wool resistance) and reliability were low.

In comparative example 17, the release agent D4 in the polymerizable composition R32 was a silicon-based release agent having no perfluoropolyether group, and therefore had low antifouling property.

In comparative example 18, the release agent D5 in the polymerizable composition R33 was a silicon-based release agent having no perfluoropolyether group, and therefore, the antifouling property, abrasion resistance, and reliability were low. Further, the transparency of the polymerizable composition R33 was also low.

In comparative example 19, the release agent D6 in the polymerizable composition R34 was a silicon-based release agent having no perfluoropolyether group, and therefore, the antifouling property, abrasion resistance, and reliability were low. Further, the transparency of the polymerizable composition R34 was also low.

In comparative example 20, the release agent D7 in the polymerizable composition R35 was a silicon-based release agent having no perfluoropolyether group, and therefore, the antifouling property, abrasion resistance, and reliability were low. Further, the transparency of the polymerizable composition R35 was also low.

In comparative example 21, the release agent D8 in the polymerizable composition R36 was a fluorine-based release agent having no perfluoropolyether group, and therefore, the stain-proofing property (water repellency) and abrasion resistance were low.

In comparative example 22, the release agent D9 in the polymerizable composition R37 was a fluorine-based release agent having no perfluoropolyether group, and therefore, the stain-proofing property (water repellency) and the abrasion resistance were low.

In comparative example 23, the release agent D10 in the polymerizable composition R38 was a fluorine-based release agent having no perfluoropolyether group, and therefore, the stain-proofing property (water repellency) and abrasion resistance were low.

[ accompanying notes ]

An aspect of the present invention may be an antifouling film including: a substrate; and a polymer layer which is disposed on the surface of the base material and has a concavo-convex structure having a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light on the surface, wherein the polymer layer is a cured product of a polymerizable composition containing, in terms of active ingredients, 15 to 40 wt% of hexafunctional or higher acrylic urethane, 35 to 60 wt% of tetrafunctional or higher polyfunctional acrylate having 3 to 15 ethylene oxide groups per functional group, 15 to 30 wt% of monofunctional acrylate having no ethylene oxide group, 0.5 to 10 wt% of a fluorine-based release agent having a perfluoropolyether group and having a fluorine atom concentration of 50 wt% or less, and 0.5 to 5 wt% of a polymerization initiator. According to this embodiment, an antifouling film having excellent antifouling properties, adhesion, abrasion resistance, and reliability can be obtained.

The coefficient of dynamic friction of the surface of the polymer layer may be 2.0 or less. According to this structure, the wear resistance is improved well.

The surface of the polymer layer may have a contact angle with water of 130 ° or more and a contact angle with hexadecane of 30 ° or more. With this structure, the antifouling property is improved.

The monofunctional acrylate may also include at least one of N-acryloyl morpholine and N, N-dimethylacrylamide. According to this structure, the viscosity of the monofunctional acrylate is reduced, and the compatibility with the urethane acrylate, the polyfunctional acrylate, and the fluorine-based release agent is further improved. Further, when the substrate is a triacetyl cellulose film, the adhesiveness is further improved.

The thickness of the polymer layer may be 5.0 μm or more and 20.0 μm or less. According to this structure, the fluorine atoms in the fluorine-based release agent are aligned at a higher concentration on the surface of the polymer layer (the surface on the opposite side from the base material).

The average pitch of the plurality of projections may be 100nm or more and 400nm or less. With this configuration, the occurrence of optical phenomena such as moire and iris unevenness can be sufficiently prevented.

The average height of the plurality of projections may be 50nm or more and 600nm or less. With this structure, the preferable average aspect ratio of the plurality of projections can be satisfied at the same time.

The average aspect ratio of the plurality of projections may be 0.8 or more and 1.5 or less. With this configuration, occurrence of optical phenomena such as moire fringes and iris unevenness can be sufficiently prevented, and excellent antireflection properties can be realized. Furthermore, the generation of sticking due to the reduction of the processability of the uneven structure and the deterioration of the transfer state when the uneven structure is formed are sufficiently prevented.

Description of the reference numerals

1 antifouling film

2 base material

3 Polymer layer

4 convex part

5 polymerizable composition

6 mould

P pitch

Thickness of the T Polymer layer

Claims

1. An antifouling film comprising:

a substrate; and

a polymer layer which is disposed on the surface of the base material and has a concavo-convex structure in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light on the surface,

the antifouling film is characterized in that the polymer layer is a cured product of a polymerizable composition,

the polymerizable composition contains, in terms of active ingredients, 15 to 40 wt% of hexafunctional or higher acrylic urethane, 35 to 60 wt% of tetrafunctional or higher polyfunctional acrylate having 3 to 15 ethylene oxide groups per functional group, 15 to 30 wt% of monofunctional acrylate having no ethylene oxide group, 0.5 to 10 wt% of a fluorine-based release agent having a perfluoropolyether group and having a fluorine atom concentration of 50 wt% or lower, and 0.5 to 5 wt% of a polymerization initiator.

2. The antifouling film according to claim 1, wherein the surface of the polymer layer has a dynamic friction coefficient of 2.0 or less.

3. The stain resistant film according to claim 1 or 2 wherein the surface of the polymer layer has a contact angle of water of 130 ° or more and a contact angle of hexadecane of 30 ° or more.

4. The soil resistant film according to claim 1 or 2 wherein the monofunctional acrylate comprises at least one of N-acryloyl morpholine and N, N-dimethylacrylamide.

5. The antifouling film according to claim 1 or 2, wherein the polymer layer has a thickness of 5.0 μm or more and 20.0 μm or less.

6. The antifouling film according to claim 1 or 2, wherein the average pitch of the plurality of projections is 100nm or more and 400nm or less.

7. The antifouling film according to claim 1 or 2, wherein the average height of the plurality of projections is 50nm or more and 600nm or less.

8. The antifouling film according to claim 1 or 2, wherein the average aspect ratio of the plurality of protrusions is 0.8 or more and 1.5 or less.